CN113363514A - Carbon aerogel supported cobalt monoatomic catalyst for metal air battery, preparation method and application thereof - Google Patents
Carbon aerogel supported cobalt monoatomic catalyst for metal air battery, preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000004966 Carbon aerogel Substances 0.000 title claims abstract description 83
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 82
- 239000010941 cobalt Substances 0.000 title claims abstract description 82
- 229910052751 metal Inorganic materials 0.000 title claims description 17
- 239000002184 metal Substances 0.000 title claims description 17
- 238000002360 preparation method Methods 0.000 title abstract description 32
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 15
- 125000004429 atom Chemical group 0.000 claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 229920001661 Chitosan Polymers 0.000 claims description 80
- 239000007864 aqueous solution Substances 0.000 claims description 59
- 238000003756 stirring Methods 0.000 claims description 55
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 33
- 239000004964 aerogel Substances 0.000 claims description 27
- 239000000017 hydrogel Substances 0.000 claims description 26
- 238000009210 therapy by ultrasound Methods 0.000 claims description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000003763 carbonization Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000000967 suction filtration Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- -1 cobalt porphyrin-cobalt acetate Chemical compound 0.000 claims description 4
- 238000009792 diffusion process Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 235000002639 sodium chloride Nutrition 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 3
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004472 Lysine Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- FDJOLVPMNUYSCM-WZHZPDAFSA-L cobalt(3+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+3].N#[C-].N([C@@H]([C@]1(C)[N-]\C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C(\C)/C1=N/C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C\C1=N\C([C@H](C1(C)C)CCC(N)=O)=C/1C)[C@@H]2CC(N)=O)=C\1[C@]2(C)CCC(=O)NC[C@@H](C)OP([O-])(=O)O[C@H]1[C@@H](O)[C@@H](N2C3=CC(C)=C(C)C=C3N=C2)O[C@@H]1CO FDJOLVPMNUYSCM-WZHZPDAFSA-L 0.000 claims description 3
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 3
- 235000018417 cysteine Nutrition 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004220 glutamic acid Substances 0.000 claims description 3
- 235000013922 glutamic acid Nutrition 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 2
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229930003779 Vitamin B12 Natural products 0.000 claims description 2
- NVJHHSJKESILSZ-UHFFFAOYSA-N [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NVJHHSJKESILSZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 235000010216 calcium carbonate Nutrition 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- OEZXFVMHAJJKKK-UHFFFAOYSA-N cobalt;1,10-phenanthroline Chemical compound [Co].C1=CN=C2C3=NC=CC=C3C=CC2=C1 OEZXFVMHAJJKKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 239000011715 vitamin B12 Substances 0.000 claims description 2
- 235000019163 vitamin B12 Nutrition 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 14
- 239000010411 electrocatalyst Substances 0.000 description 13
- 239000002105 nanoparticle Substances 0.000 description 12
- 238000007710 freezing Methods 0.000 description 11
- 230000008014 freezing Effects 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000006196 deacetylation Effects 0.000 description 9
- 238000003381 deacetylation reaction Methods 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 238000004108 freeze drying Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011245 gel electrolyte Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910021524 transition metal nanoparticle Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9008—Organic or organo-metallic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
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- Manufacturing & Machinery (AREA)
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- Catalysts (AREA)
Abstract
The invention relates to a carbon aerogel supported cobalt monoatomic catalyst for a metal-air battery, belonging to the technical field of metal-air batteries. The catalyst carrier is porous carbon aerogel, and the specific surface area of the porous carbon aerogel is 100-800 m2g‑1The pore diameter is 2-100 nm, and the pore volume is 0.05-1.0 cm3g‑1The active component is a cobalt monoatomic atom which is uniformly distributed on the surface of the porous carbon aerogel and coordinated with the heteroatom; the catalyst comprises the following components: the content of the porous carbon aerogel is 67-95.95 wt%, the content of the cobalt monoatomic atom is 0.05-8.0 wt%, and the content of the heteroatom is 4-25 wt%. The catalyst has high content of cobalt monoatomic atom, uniform dispersion and stable physicochemical structure. The preparation method is green and simple and has low cost; the catalyst is applied to a metal-air battery, has excellent charge-discharge efficiency and cycle life, and has performance superior to that of a commercial Pt/C catalyst.
Description
Technical Field
The invention belongs to the technical field of metal-air batteries, and particularly relates to a carbon aerogel supported cobalt monoatomic catalyst for a metal-air battery, a preparation method and application thereof.
Background
With the increasing global energy and environmental crisis, the development of environmentally friendly energy conversion and storage devices is receiving more and more attention. Among them, metal-air batteries are receiving attention because of their environmental friendliness, abundant resources, high safety, and high energy density. However, the metal-air battery has a problem of slow kinetics of an Oxygen Reduction Reaction (ORR) during discharge, resulting in short cycle life, low energy efficiency, high overpotential, and the like. It is well known that noble metal Pt-based nanocatalysts have excellent electrocatalytic ORR activity, but their reserves are rare, cost is high, methanol resistance is poor, and particularly their poor stability severely hinders their practical application. Therefore, it is crucial and significant to develop an efficient, economical and stable non-noble metal catalyst for electrocatalytic ORR instead of Pt-based catalyst.
In order to solve the above problems, transition metal oxide particles have been developed as ORR electrocatalysts in the prior art. For example, the nano-catalysts represented by Co, Fe, Ni and the like reported in chinese patents CN 107308977A, CN 111785977a and CN 106450357 a are all cheap, abundant in reserves and excellent in ORR catalytic activity. However, the transition metal nanoparticles still have the defects of low utilization rate of metal atoms, small specific surface area, poor conductivity and the like when used as the ORR electrocatalyst. Compared with transition metal nano-particles and nano-clusters, the transition metal monatomic catalyst has absolute advantages in electrocatalysis ORR due to the characteristics of high atom utilization rate, high catalysis efficiency, uniform active sites and the like. The transition metal single atom is loaded on the carbon-based carrier (such as graphene, carbon nano tube, graphite carbon and carbon aerogel, etc.) with excellent conductivity, so that the problem of poor conductivity of the catalyst can be solved, and the stability of the transition metal atom and the specific surface area of the composite catalyst can be improved. Therefore, the research on the transition metal single-atom catalyst loaded on the carbon-based carrier has important significance for developing the high-efficiency ORR electrocatalyst. The carbon aerogel has good conductivity, large specific surface area and good chemical stability, and is a good carrier of the metal monatomic catalyst.
The chitosan is a biomass resource with abundant natural reserves, can be regenerated and degraded, can form hydrogel when meeting metal ions, and can form chitosan-metal ion aerogel after freeze drying, wherein the aerogel is an excellent carbon aerogel precursor. At present, various journals at home and abroad are reported to be made of chitosan and inorganic cobalt salt (CoCl)2、Co(NO3)2) The preparation method for preparing the carbon aerogel supported cobalt-based catalyst for the precursor and the application of the carbon aerogel supported cobalt-based catalyst in electrocatalytic oxygen reduction are adopted, but when the chitosan-cobalt ion aerogel is subjected to heat treatment at high temperature, cobalt atoms can be agglomerated to form cobalt sulfide or cobalt oxide nanoparticles and the like, so that a single cobalt atom active site is difficult to generate. According to the reference literature, the research of using chitosan and cobalt macrocyclic compound or cobalt-organic ligand complex as a carbon source and a cobalt source to prepare carbon aerogel supported cobalt monoatomic catalyst as an ORR catalyst has not been reported, and the catalyst is expected to be applied to metal air batteries.
Disclosure of Invention
In view of the above situation, an object of the present invention is to provide a carbon aerogel supported cobalt monatomic catalyst for a metal-air battery, which can improve the utilization rate and mass transfer capacity of cobalt atoms, and in which the cobalt atoms can stably exist on a porous carbon aerogel carrier, the catalytic efficiency is high, and the catalytic stability is good. Meanwhile, the invention also provides a preparation method of the catalyst, the preparation method fully utilizes biomass chitosan with wide sources as a carbon source, takes rich cobalt as a raw material, has low cost, can realize large-scale preparation of the cobalt single-atom catalyst, and has simple operation process.
The invention is realized by the following technical scheme:
a carbon aerogel supported cobalt monoatomic catalyst for a metal air battery is characterized in that a catalyst carrier is porous carbon aerogel, and the specific surface area of the porous carbon aerogel is 100-800 m2g-1The pore diameter is 2-100 nm, and the pore volume is 0.05-1.0 cm3g-1The active component is a cobalt monoatomic atom which is uniformly distributed on the surface of the porous carbon aerogel and coordinated with the heteroatom; the catalyst comprises the following components: the content of the porous carbon aerogel is 67-95.95 wt%, the content of the cobalt monoatomic atom is 0.05-8.0 wt%, and the content of the heteroatom is 4-25 wt%.
The preparation method of the carbon aerogel supported cobalt monoatomic catalyst for the metal-air battery comprises the following steps:
(1) synthesis of chitosan hybrid hydrogel: dissolving chitosan in an acetic acid aqueous solution, stirring uniformly to obtain a chitosan aqueous solution, then adding a pore-forming agent, stirring uniformly, slowly dropwise adding a heteroatom-containing precursor solution and a cobalt precursor solution into the uniformly mixed system under stirring, and performing ultrasonic treatment after stirring uniformly until a chitosan heterozygosis hydrogel is obtained;
(2) performing vacuum freeze drying on the chitosan hybrid hydrogel prepared in the step (1) to obtain chitosan hybrid aerogel;
(3) carbonizing the chitosan hybrid aerogel obtained in the step (2) at high temperature under the protection of inert atmosphere to enable cobalt atoms and nitrogen atoms to generate coordination reaction in a high-temperature environment;
(4) and (3) soaking in an acid solution to remove the pore-forming agent, repeatedly performing suction filtration and washing with deionized water to neutrality, and finally drying to obtain the carbon aerogel supported cobalt monoatomic catalyst for the metal air battery.
As a preferred technical scheme, in the preparation method, in the step (1), the mass fraction of the chitosan aqueous solution is 1-3%; the acetic acid aqueous solution is 2-5% by mass; the heteroatom precursor comprises one or more of lysine, cysteine, urea, thiourea, ethylenediamine, dicyandiamide, melamine and glutamic acid; the precursor solution containing the heteroatom is an aqueous solution or an organic solution with the mass percentage concentration of 15-25%.
As a preferred technical solution, for the above preparation method, in step (1), the cobalt precursor includes, but is not limited to, one or more of cobalt-based ionic liquid, vitamin B12 (aka: cobalamin), cobalt porphyrin, cobalt phthalocyanine, porphyrin-cobalt acetate complex, cobalt-phenanthroline complex, and cobalt sulfonated phthalocyanine; the cobalt precursor solution is an aqueous solution or an organic solution with the mass percentage concentration of 4-14%.
As a preferred technical solution, for the above preparation method, in step (1), the pore-forming agent includes, but is not limited to, one or more of silicon dioxide, calcium carbonate, sodium carbonate, zinc chloride, and sodium chloride; the mass fraction of the pore-forming agent is 1-5%.
As a preferred technical solution, for the above preparation method, in step (2), the chitosan hybrid aerogel consists of the following precursors in percentage by mass:
and (3) chitosan: 1 to 5 weight percent,
pore-forming agent: 1 to 5 weight percent,
heteroatom-containing precursors: 77 wt% -95 wt%,
cobalt precursor: 3 wt% -13 wt%.
As a preferable technical scheme, in the preparation method, in the step (3), the inert atmosphere is high-purity nitrogen or high-purity argon; the high-temperature carbonization comprises the following steps: the first step is as follows: heating the mixture from room temperature to T, wherein T is 700-1000 ℃, the heating rate is 4-8 ℃/min, and the second step is as follows: keeping the temperature T constant for 1-3 h, and the third step: and cooling the temperature from T to room temperature at a cooling rate of 4-10 ℃/min.
As a preferable technical solution, in the above preparation method, in the step (4), the acid solution is at least one of a hydrofluoric acid aqueous solution, a hydrochloric acid aqueous solution, a nitric acid aqueous solution, and a sulfuric acid aqueous solution; the acid solution is 0.5-2 mol/L, the acid soaking time is 12-24 h, and the acid soaking temperature is 60-100 ℃.
Preferably, in the preparation method, in the step (1), the stirring mode is mechanical stirring or magnetic stirring, and the stirring temperature is 5-30 ℃; the ultrasonic treatment temperature is 5-40 ℃, the ultrasonic treatment time is 2-5 h, and the ultrasonic treatment frequency is 100-1200W.
Preferably, in the preparation method, in the step (2), the vacuum freeze drying step is to freeze the mixture at-25 to-55 ℃ for 5 to 12 hours and then dry the mixture for 24 to 48 hours in a vacuum environment of 0.0 to 10 MPa.
Preferably, in the preparation method, in the step (4), the drying mode is freeze drying or vacuum drying, the pressure during the freeze drying is 0.0-10 Mpa, the drying temperature is-25-55 ℃, and the drying time is 24-48 h, the pressure during the vacuum drying is-0.5-1 Mpa, the drying temperature is 60-120 ℃, and the drying time is 8-12 h.
The preparation method provided by the invention is simple to operate, the raw materials such as chitosan, sulfonated cobalt phthalocyanine, urea and the like are cheap and easy to obtain, the preparation conditions are mild, the large-scale production can be realized, and the method is easy to apply and popularize in actual industry.
The carbon aerogel supported cobalt monoatomic catalyst for the metal air battery, which is prepared by the invention, has the advantages that the cobalt monoatomic and nitrogen atoms are coordinated and uniformly and stably distributed on the porous carbon aerogel carrier, so that the utilization rate and the stability of the cobalt monoatomic can be improved.
The carbon aerogel supported cobalt monoatomic catalyst for the metal air battery, which is prepared by the invention, can realize accurate and effective regulation and control of a coordination structure between a cobalt monoatomic atom and a heteroatom (nitrogen atom), and can realize effective regulation and control of electron density around the cobalt monoatomic atom.
Further, the invention also provides application of the carbon aerogel supported cobalt monoatomic catalyst for the metal-air battery in electrocatalytic oxygen reduction.
Furthermore, the invention also provides a metal-air battery, which comprises an air anode, a diaphragm, electrolyte and a metal cathode, wherein the air anode comprises a gas diffusion layer, a current collector layer and a catalyst layer, the catalyst adopts the carbon aerogel supported cobalt monatomic catalyst for the metal-air battery, the performance of the catalyst is superior to that of a commercial Pt/C catalyst, and the requirement of industrial production and application can be met.
The metal-air battery is characterized in that the metal-air battery comprises a battery body and a battery cover, wherein the battery cover is provided with a metal layer and a metal layer. The zinc-air cell tests include, but are not limited to: the carbon aerogel supported cobalt monoatomic catalyst for the metal-air battery is used as an air anode catalyst, a cathode is a metal zinc sheet, and electrolyte is 6 mol/L KOH +0.2 mol/L zinc acetate aqueous solution or gel electrolyte thereof.
The invention has the following beneficial effects:
(1) according to the carbon aerogel supported cobalt monoatomic catalyst for the metal air battery, disclosed by the invention, the cobalt monoatomic atoms and the nitrogen atoms are coordinated and anchored on the porous carbon aerogel carrier, so that the catalyst has a stable physicochemical structure, the cobalt monoatomic atoms are uniformly dispersed and high in content, and the utilization rate of the cobalt atoms and the catalytic stability are improved.
(2) The preparation method of the carbon aerogel supported cobalt monoatomic catalyst for the metal-air battery is simple, and the cobalt sulfonated phthalocyanine, nitrogen atoms and chitosan hydrogel are cooperatively protected, so that the cobalt atoms are prevented from being aggregated in the high-temperature carbonization process, and the cobalt atoms are monodisperse and positioned.
(3) According to the carbon aerogel supported cobalt monatomic catalyst for the metal air battery, the specific surface area and the pore size structure of the carbon aerogel are regulated and controlled by using the pore-forming agent during preparation, the porous carbon aerogel is used as a carrier of the cobalt monatomic, the catalyst has rich hierarchical pore structures, the mass transfer capacity is favorably improved, the catalyst has a larger specific surface area, the number of active sites is favorably increased, and the catalytic activity is further improved.
(4) The carbon aerogel supported cobalt monoatomic catalyst for the metal-air battery can be applied to the metal-air battery such as a zinc-air battery, and has excellent charge-discharge efficiency and cycle life.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings used in the embodiments or the prior art descriptions will be briefly introduced, wherein the drawings are used for providing further explanation of the present invention and form a part of the present application, and the exemplary embodiments and the explanation of the present invention are used for explaining the present invention and do not form a limitation to the present invention.
Fig. 1 is a Scanning Transmission Electron Microscope (STEM) photograph of a carbon aerogel supported cobalt monoatomic catalyst for a metal-air battery according to example 1.
Fig. 2 is an XRD characterization of the carbon aerogel supported cobalt monatomic catalyst for the metal-air cell of example 1.
Fig. 3 is a BET characterization of the carbon aerogel supported cobalt monatomic catalyst for metal-air cells of example 1.
Fig. 4 is a Cyclic Voltammetry (CV) curve for electrocatalytic oxygen reduction of a carbon aerogel-supported cobalt monatomic catalyst for a metal-air cell of example 1.
Fig. 5 is a Linear Scan (LSV) curve of electrocatalytic oxygen reduction of a carbon aerogel supported cobalt monatomic catalyst for a metal-air cell of example 1.
Fig. 6 is a methanol resistance test of carbon aerogel supported cobalt monatomic catalyst and commercial Pt/C electrocatalytic oxygen reduction for metal-air cells of example 1.
Fig. 7 is a stability test of electrocatalytic oxygen reduction of the carbon aerogel-supported cobalt monatomic catalyst for metal-air batteries of example 1.
Fig. 8 is an open circuit potential test of the carbon aerogel supported cobalt monatomic catalyst for metal-air cells and commercial Pt/C applied to a zinc-air cell of example 1.
Fig. 9 is a specific capacity test of the carbon aerogel supported cobalt monatomic catalyst for a metal-air battery of example 1 applied to a zinc-air battery.
Fig. 10 is a charge and discharge curve of the carbon aerogel-supported cobalt monatomic catalyst for a metal-air battery of example 1 applied to a zinc-air battery.
Detailed Description
In order that those skilled in the art will better understand the present invention, a more complete and complete description of the present invention is provided below in conjunction with the accompanying drawings and embodiments. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
Example 1
A preparation method of a carbon aerogel supported cobalt monatomic catalyst for a metal-air battery comprises the following steps:
(1) weighing 78 mg of chitosan (the viscosity is 100-200 mpa.s, the deacetylation degree is more than or equal to 95%) to be dissolved in 7.7 ml of 2 wt% acetic acid aqueous solution, uniformly stirring at room temperature to obtain chitosan aqueous solution, then adding 78 mg of silicon dioxide pore forming agent, after uniformly stirring, adding 41 ml of aqueous solution in which 7.41 g of urea is dissolved, continuously and slowly dropwise adding 5.6 ml of aqueous solution 0 in which 234 mg of sulfonated cobalt phthalocyanine is dissolved after uniformly stirring, continuously stirring for 1 h, and ultrasonically removing bubbles for 2 h until chitosan heterozygous hydrogel is obtained; wherein the stirring temperature is 5 ℃, the ultrasonic treatment temperature is 15 ℃, and the ultrasonic treatment frequency is 800W; (2) freezing the chitosan hybrid hydrogel obtained in the step (1) in a freezing dryer at-45 ℃ for 12 h, and drying for 24h under a vacuum environment of 10 Mpa to obtain chitosan hybrid aerogel; (3) placing the chitosan hybrid aerogel obtained in the step (2) in a tubular furnace, carrying out high-temperature carbonization treatment under the protection of high-purity argon (the gas flow rate is 5 ml/min), heating to 800 ℃ at the speed of 4 ℃/min, roasting for 2 h, and then cooling to room temperature at the speed of 5 ℃/min; (4) and (3) putting the sample obtained in the step (3) into 0.5 mol/L hydrofluoric acid solution at 80 ℃ to remove silicon dioxide nano particles, then washing the sample to be neutral by using deionized water through suction filtration, and drying the sample in vacuum at-0.5 Mpa at 100 ℃ for 12 hours to obtain the carbon aerogel supported Co single-atom electrocatalyst, which is marked as Co SA-N-S/C-800.
The carbon aerogel loaded with Co monatomics is characterized by adopting a Scanning Transmission Electron Microscope (STEM), and as can be seen from the attached figure 1, Co is uniformly dispersed on the surface of the porous carbon aerogel in a monodisperse atomic form. When the catalyst is detected by XRD, as can be seen from the XRD result shown in figure 2, the obtained catalyst does not find a diffraction peak of Co-based nanoparticles, and Co is dispersed on the porous carbon aerogel in a monoatomic form. The catalyst was characterized by BET, and as can be seen from the BET results in FIG. 3, the resulting catalyst had a specific surface area of 145 m2g-1The pore diameter structure is 2 nm-100 nm.
Example 2
A preparation method of a carbon aerogel supported cobalt monatomic catalyst for a metal-air battery comprises the following steps:
(1) weighing 390 mg of chitosan (the viscosity is 100-200 mpa.s, the deacetylation degree is more than or equal to 95%) and dissolving in 19.11 ml of 2 wt% acetic acid aqueous solution, uniformly stirring at room temperature to obtain a chitosan aqueous solution, then adding 390 mg of sodium chloride pore-forming agent, after uniformly stirring, adding 18.1 ml of aqueous solution in which 6.006 g of urea is dissolved, continuously and slowly dropwise adding 12 ml of aqueous solution in which 1.014 g of sulfonated cobalt phthalocyanine is dissolved after uniformly stirring, continuously stirring for 1 h, and ultrasonically removing bubbles for 5 h until chitosan hybrid hydrogel is obtained; wherein the stirring temperature is 15 ℃, the ultrasonic treatment temperature is 20 ℃, and the ultrasonic treatment frequency is 100W; (2) freezing the chitosan hybrid hydrogel obtained in the step (1) in a freeze dryer at-55 ℃ for 10 h, and drying for 36 h in a vacuum environment of 8 Mpa to obtain chitosan hybrid aerogel; (3) placing the chitosan hybrid aerogel obtained in the step (2) in a tubular furnace, carrying out high-temperature carbonization treatment under the protection of high-purity argon (the gas flow rate is 5 ml/min), heating to 1000 ℃ at the speed of 4 ℃/min, roasting for 2 h, and then cooling to room temperature at the speed of 5 ℃/min; (4) and (3) putting the sample obtained in the step (3) into a sulfuric acid solution with the concentration of 2 mol/L and the temperature of 60 ℃ to remove Co-based nano particles which are possibly generated, then washing the sample to be neutral by using deionized water through suction filtration, and drying the sample in vacuum for 8 hours at the temperature of-1 Mpa and the temperature of 120 ℃ to obtain the carbon aerogel supported Co single-atom electrocatalyst which is marked as Co SA-N-S/C-1000.
Example 3
A preparation method of a carbon aerogel supported cobalt monatomic catalyst for a metal-air battery comprises the following steps:
(1) weighing 78 mg of chitosan (the viscosity is 100-200 mpa.s, the deacetylation degree is more than or equal to 95%) to be dissolved in 7.7 ml of 2 wt% acetic acid aqueous solution, uniformly stirring at room temperature to obtain a chitosan aqueous solution, then adding 234 mg of sodium carbonate pore-forming agent, after uniformly stirring, adding 27 ml of aqueous solution in which 6.708g of thiourea is dissolved, continuously and slowly dropwise adding 7 ml of aqueous solution in which 780 mg of sulfonated cobalt phthalocyanine after uniformly stirring, continuously stirring for 1 h, and removing bubbles by ultrasound for 3 h until chitosan heterozygosis hydrogel is obtained; wherein the stirring temperature is 25 ℃, the ultrasonic treatment temperature is 35 ℃, and the ultrasonic treatment frequency is 1200W; (2) freezing the chitosan hybrid hydrogel obtained in the step (1) in a freeze dryer at-45 ℃ for 8 h, and drying for 48 h in a vacuum environment of 5 Mpa to obtain chitosan hybrid aerogel; (3) placing the chitosan hybrid aerogel obtained in the step (2) in a tubular furnace, carrying out high-temperature carbonization treatment under the protection of high-purity argon (the gas flow rate is 5 ml/min), heating to 800 ℃ at the speed of 4 ℃/min, roasting for 2 h, and then cooling to room temperature at the speed of 5 ℃/min; (4) and (3) putting the sample obtained in the step (3) into 0.5 mol/L sulfuric acid solution at 100 ℃ to remove Co-based nano particles possibly generated, then washing the sample to be neutral by using deionized water through suction filtration, and drying the sample in vacuum at-1 Mpa and 60 ℃ for 10 hours to obtain the carbon aerogel supported Co monoatomic electrocatalyst.
Example 4
A preparation method of a carbon aerogel supported cobalt monatomic catalyst for a metal-air battery comprises the following steps:
(1) weighing 78 mg of chitosan (the viscosity is 100-200 mpa.s, the deacetylation degree is more than or equal to 95%) to be dissolved in 7.7 ml of 3 wt% acetic acid aqueous solution, uniformly stirring at room temperature to obtain a chitosan aqueous solution, then adding 390 mg of calcium carbonate pore-forming agent, after uniformly stirring, adding 27 ml of aqueous solution in which 6.708g of dicyandiamide is dissolved, continuously and slowly dropwise adding 3.85 ml of aqueous solution in which 624 mg of sulfonated cobalt phthalocyanine is dissolved after uniformly stirring, continuously stirring for 1 h, and removing bubbles by ultrasound for 2 h until chitosan hybrid hydrogel is obtained; wherein the stirring temperature is 8 ℃, the ultrasonic treatment temperature is 5 ℃, and the ultrasonic treatment frequency is 1000W; (2) freezing the chitosan hybrid hydrogel obtained in the step (1) in a freeze dryer at-50 ℃ for 12 h, and drying for 24h under a vacuum environment of 0.0 Mpa to obtain the chitosan hybrid aerogel; (3) placing the chitosan hybrid aerogel obtained in the step (2) in a tubular furnace, carrying out high-temperature carbonization treatment under the protection of high-purity argon (the gas flow rate is 5 ml/min), heating to 800 ℃ at the speed of 4 ℃/min, roasting for 2 h, and then cooling to room temperature at the speed of 5 ℃/min; (4) and (4) putting the sample obtained in the step (3) into 0.5 mol/L sulfuric acid solution at 80 ℃ to remove Co-based nano particles possibly generated, then washing the sample to be neutral by using deionized water through suction filtration, and drying the sample in vacuum at 100 ℃ under-0.5 Mpa for 12 hours to obtain the carbon aerogel supported Co monoatomic electrocatalyst.
Example 5
A preparation method of a carbon aerogel supported cobalt monatomic catalyst for a metal-air battery comprises the following steps:
(1) weighing 234 mg of chitosan (the viscosity is 100-200 mpa.s, the deacetylation degree is more than or equal to 95%) and dissolving in 7.6 ml of 3 wt% acetic acid aqueous solution, uniformly stirring at room temperature to obtain a chitosan aqueous solution, then adding 234 mg of zinc chloride pore-forming agent, after uniformly stirring, adding 27 ml of aqueous solution in which 6.708g of urea is dissolved, continuously and slowly dropwise adding 3.85 ml of aqueous solution in which 624 mg of sulfonated cobalt phthalocyanine is dissolved after uniformly stirring, continuously stirring for 1 h, and removing bubbles by ultrasound for 3 h until obtaining the chitosan heterozygous hydrogel; wherein the stirring temperature is 30 ℃, the ultrasonic treatment temperature is 10 ℃, and the ultrasonic treatment frequency is 300W; (2) freezing the chitosan hybrid hydrogel obtained in the step (1) in a freeze dryer at-30 ℃ for 5 h, and drying for 24h under a vacuum environment of 2Mpa to obtain chitosan hybrid aerogel; (3) placing the chitosan hybrid aerogel obtained in the step (2) in a tubular furnace, carrying out high-temperature carbonization treatment under the protection of high-purity argon (the gas flow rate is 5 ml/min), heating to 700 ℃ at the speed of 8 ℃/min, roasting for 3 h, and then cooling to room temperature at the speed of 4 ℃/min; (4) and (4) putting the sample obtained in the step (3) into 0.5 mol/L sulfuric acid solution at 80 ℃ to remove Co-based nano particles possibly generated, then washing the sample to be neutral by using deionized water through suction filtration, and drying the sample in vacuum at 100 ℃ under-0.5 Mpa for 12 hours to obtain the carbon aerogel supported Co monoatomic electrocatalyst.
Example 6
A preparation method of a carbon aerogel supported cobalt monatomic catalyst for a metal-air battery comprises the following steps:
(1) weighing 234 mg of chitosan (the viscosity is 100-200 mpa.s, the deacetylation degree is more than or equal to 95%) and dissolving in 7.6 ml of 3 wt% acetic acid aqueous solution, uniformly stirring at room temperature to obtain a chitosan aqueous solution, then adding 78 mg of calcium carbonate pore-forming agent, after uniformly stirring, adding 27 ml of aqueous solution in which 6.708g of ethylenediamine is dissolved, continuously and slowly dropwise adding 7 ml of aqueous solution in which 780 mg of sulfonated cobalt phthalocyanine is dissolved after uniformly stirring, continuously stirring for 1 h, and ultrasonically removing bubbles for 4h until chitosan hybrid hydrogel is obtained; wherein the stirring temperature is 20 ℃, the ultrasonic treatment temperature is 40 ℃, and the ultrasonic treatment frequency is 500W; (2) freezing the chitosan hybrid hydrogel obtained in the step (1) in a freeze dryer at-25 ℃ for 12 h, and drying for 24h under a vacuum environment of 5 Mpa to obtain chitosan hybrid aerogel; (3) placing the chitosan hybrid aerogel obtained in the step (2) in a tubular furnace, carrying out high-temperature carbonization treatment under the protection of high-purity argon (the gas flow rate is 5 ml/min), heating to 800 ℃ at the speed of 4 ℃/min, roasting for 2 h, and then cooling to room temperature at the speed of 5 ℃/min; (4) and (4) putting the sample obtained in the step (3) into 0.5 mol/L sulfuric acid solution at 80 ℃ to remove Co-based nano particles possibly generated, then washing the sample to be neutral by using deionized water through suction filtration, and freeze-drying the sample at 0.0 Mpa and-55 ℃ for 24 hours to obtain the carbon aerogel supported Co monoatomic electrocatalyst.
Example 7
A preparation method of a carbon aerogel supported cobalt monatomic catalyst for a metal-air battery comprises the following steps:
(1) weighing 390 mg of chitosan (the viscosity is 100-200 mpa.s, the deacetylation degree is more than or equal to 95%) and dissolving in 19.11 ml of 5 wt% acetic acid aqueous solution, uniformly stirring at room temperature to obtain a chitosan aqueous solution, then adding 78 mg of silicon dioxide pore forming agent, after uniformly stirring, adding 19 ml of aqueous solution in which 6.318 g of cysteine is dissolved, continuously and slowly dropwise adding 12 ml of aqueous solution in which 1.014 g of sulfonated cobalt phthalocyanine is dissolved after uniformly stirring, continuously stirring for 1 h, and ultrasonically removing bubbles for 5 h until chitosan hybrid hydrogel is obtained; wherein the stirring temperature is 18 ℃, the ultrasonic treatment temperature is 25 ℃, and the ultrasonic treatment frequency is 700W; (2) freezing the chitosan hybrid hydrogel obtained in the step (1) in a freezing dryer at-45 ℃ for 10 h, and drying in a vacuum environment of 3 Mpa for 48 h to obtain chitosan hybrid aerogel; (3) placing the chitosan hybrid aerogel obtained in the step (2) in a tubular furnace, carrying out high-temperature carbonization treatment under the protection of high-purity argon (the gas flow rate is 5 ml/min), heating to 700 ℃ at the speed of 6 ℃/min, roasting for 1 h, and then cooling to room temperature at the speed of 10 ℃/min; (4) and (4) putting the sample obtained in the step (3) into 0.5 mol/L80 ℃ hydrofluoric acid solution to remove silicon dioxide nano particles and Co-based nano particles possibly generated, then washing the sample to be neutral by deionized suction filtration, and freeze-drying the sample at 10 Mpa and-25 ℃ for 48 hours to obtain the carbon aerogel supported Co monoatomic electrocatalyst.
Example 8
A preparation method of a carbon aerogel supported cobalt monatomic catalyst for a metal-air battery comprises the following steps:
(1) weighing 390 mg of chitosan (the viscosity is 100-200 mpa.s, the deacetylation degree is more than or equal to 95%) and dissolving in 19.11 ml of 5 wt% acetic acid aqueous solution, uniformly stirring at room temperature to obtain a chitosan aqueous solution, then adding 234 mg of calcium carbonate pore-forming agent, after uniformly stirring, adding 39 ml of aqueous solution in which 6.942 g of lysine is dissolved, continuously and slowly dropwise adding 5.6 ml of aqueous solution in which 234 mg of sulfonated cobalt phthalocyanine is dissolved after uniformly stirring, continuously stirring for 1 h, and ultrasonically removing bubbles for 5 h until chitosan hybrid hydrogel is obtained; wherein the stirring temperature is 10 ℃, the ultrasonic treatment temperature is 30 ℃, and the ultrasonic treatment frequency is 900W; (2) freezing the chitosan hybrid hydrogel obtained in the step (1) in a freeze dryer at-35 ℃ for 12 h, and drying for 36 h in a vacuum environment of 8 Mpa to obtain chitosan hybrid aerogel; (3) placing the chitosan hybrid aerogel obtained in the step (2) in a tubular furnace, carrying out high-temperature carbonization treatment under the protection of high-purity argon (the gas flow rate is 5 ml/min), heating to 900 ℃ at the speed of 4 ℃/min, roasting for 2 h, and then cooling to room temperature at the speed of 5 ℃/min; (4) and (3) putting the sample obtained in the step (3) into 0.5 mol/L sulfuric acid solution at 80 ℃ to remove Co-based nano particles possibly generated, then washing the sample to be neutral by using deionized water through suction filtration, and freeze-drying the sample at 50 Mpa and 35 ℃ below zero for 36 hours to obtain the carbon aerogel supported Co monoatomic electrocatalyst.
Example 9
A preparation method of a carbon aerogel supported cobalt monatomic catalyst for a metal-air battery comprises the following steps:
(1) weighing 234 mg of chitosan (the viscosity is 100-200 mpa.s, the deacetylation degree is more than or equal to 95%) and dissolving in 7.6 ml of 5 wt% acetic acid aqueous solution, uniformly stirring at room temperature to obtain a chitosan aqueous solution, then adding 390 mg of sodium chloride pore-forming agent, after uniformly stirring, adding 19 ml of aqueous solution in which 6.552 g of glutamic acid is dissolved, continuously and slowly dropwise adding 3.85 ml of aqueous solution in which 624 mg of sulfonated cobalt phthalocyanine is dissolved after uniformly stirring, continuously stirring for 1 h, and removing bubbles by ultrasonic treatment for 4h until obtaining the chitosan heterozygous hydrogel; wherein the stirring temperature is 22 ℃, the ultrasonic treatment temperature is 12 ℃, and the ultrasonic treatment frequency is 600W; (2) freezing the chitosan hybrid hydrogel obtained in the step (1) in a freeze dryer at-55 ℃ for 12 h, and drying for 24h under a vacuum environment of 10 Mpa to obtain chitosan hybrid aerogel; (3) placing the chitosan hybrid aerogel obtained in the step (2) in a tubular furnace, carrying out high-temperature carbonization treatment under the protection of high-purity argon (the gas flow rate is 5 ml/min), heating to 1000 ℃ at the speed of 4 ℃/min, roasting for 2 h, and then cooling to room temperature at the speed of 5 ℃/min; (4) and (3) putting the sample obtained in the step (3) into 0.5 mol/L sulfuric acid solution at 80 ℃ to remove Co-based nano particles possibly generated, then washing the sample to be neutral by using deionized water through suction filtration, and freeze-drying the sample at 50 Mpa and 35 ℃ below zero for 36 hours to obtain the carbon aerogel supported Co monoatomic electrocatalyst.
The carbon aerogel supported cobalt monoatomic catalyst for the metal-air battery is subjected to an electrocatalytic oxygen reduction performance test:
the three-electrode system test was performed using the Shanghai Chenghua electrochemical workstation (CHI 760E). The carbon aerogel Co-loaded monatomic electrocatalyst mixed slurry prepared in examples 1 to 9 was dropped on a rotating disk glassy carbon electrode, and after being naturally dried, it was used as a working electrode, a Pt wire was used as a counter electrode, the reference electrode was an Ag/AgCl electrode, and the electrolyte was 0.1 mol/L KOH aqueous solution. Mixing the slurry: 4 mg catalyst, 800 ml isopropanol, 200 ml water and 10 uL Nafion.
The test results are shown in FIGS. 4-7. The catalyst prepared by the invention has excellent electrocatalytic oxygen reduction performance. As can be seen from FIG. 4, O2The saturated electrolyte has a distinct cathodic oxygen reduction peak, whereas in N2The curve in the saturated electrolyte is approximately rectangular, no significant oxygen reduction peak is found. This means thatO2The carbon aerogel supported Co single-atom catalyst has catalytic oxygen reduction performance. FIG. 5 is a LSV curve of the prepared catalyst for electrocatalytic oxygen reduction at different rotational speeds. It can be seen from the graph that the limiting current density increases with increasing rotation speed, which is mainly due to the increase in the diffusion rate of oxygen in the electrolyte with increasing rotation speed. As can be seen from FIG. 6, the catalyst has very good methanol resistance. As can be seen from FIG. 7, the catalyst has very good cycle stability, catalyzes O2The reduction is carried out for 24h, and the current density is basically kept unchanged.
The carbon aerogel supported cobalt monoatomic catalyst for the metal-air battery is subjected to zinc-air battery performance test:
the performance test of the zinc-air battery adopts a gas diffusion layer added with carbon aerogel loaded Co monatomic catalyst as an air anode, a polished zinc sheet as a cathode and an electrolyte of a mixed aqueous solution of 6 mol/L KOH and 0.2 mol/L zinc acetate or a gel electrolyte thereof. Air cathode preparation 4 mg of catalyst was loaded at 2 x 2 cm using methods conventional in the art2The electrode composite substrate comprises foamed nickel, a waterproof diaphragm and conductive carbon paper.
The catalyst prepared by the invention can be used as a cathode catalyst of a zinc-air battery. Figure 8 shows the open circuit potential of the catalyst prepared by the invention applied to a zinc-air battery. The open circuit potential of the catalyst of the present invention is higher than that of the commercial Pt/C catalyst. The specific capacity of the catalyst is 771 mAhg -1751 mAhg higher than commercial catalyst-1(see FIG. 9). FIG. 10 shows the charge and discharge curves of the catalyst of the invention as a cathode catalyst, from which it can be seen that: at a current density of 10 mAcm-2The catalyst of the present invention has excellent cyclic charge and discharge performance superior to that of commercial catalyst.
The technical solutions in the embodiments of the present invention are clearly and completely described above, and the described embodiments are only a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. A carbon aerogel supported cobalt monoatomic catalyst for a metal-air battery is characterized in that: the catalyst carrier is porous carbon aerogel, and the specific surface area of the porous carbon aerogel is 100-800 m2g-1The pore diameter is 2-100 nm, and the pore volume is 0.05-1.0 cm3g-1The active component is a cobalt monoatomic atom which is uniformly distributed on the surface of the porous carbon aerogel and coordinated with the heteroatom; the catalyst comprises the following components: the content of the porous carbon aerogel is 67-95.95 wt%, the content of the cobalt monoatomic atom is 0.05-8.0 wt%, and the content of the heteroatom is 4-25 wt%.
2. A method for preparing a carbon aerogel supported cobalt monatomic catalyst for a metal-air battery according to claim 1, which comprises the steps of:
(1) synthesis of chitosan hybrid hydrogel: dissolving chitosan in an acetic acid aqueous solution, stirring uniformly to obtain a chitosan aqueous solution, then adding a pore-forming agent, stirring uniformly, slowly dropwise adding a heteroatom-containing precursor solution and a cobalt precursor solution into the uniformly mixed system under stirring, and performing ultrasonic treatment after stirring uniformly until a chitosan heterozygosis hydrogel is obtained;
(2) performing vacuum freeze drying on the chitosan hybrid hydrogel prepared in the step (1) to obtain chitosan hybrid aerogel;
(3) carbonizing the chitosan hybrid aerogel obtained in the step (2) at high temperature under the protection of inert atmosphere to enable cobalt atoms and nitrogen atoms to generate coordination reaction in a high-temperature environment;
(4) and (3) soaking in an acid solution to remove the pore-forming agent, repeatedly performing suction filtration and washing with deionized water to neutrality, and finally drying to obtain the carbon aerogel supported cobalt monoatomic catalyst for the metal air battery.
3. The method for preparing a carbon aerogel supported cobalt monatomic catalyst for a metal-air battery according to claim 2, characterized in that: in the step (1), the mass fraction of the chitosan aqueous solution is 1% -3%; the acetic acid aqueous solution is 2-5% by mass; the heteroatom precursor is one or more of lysine, cysteine, urea, thiourea, ethylenediamine, dicyandiamide, melamine and glutamic acid; the precursor solution containing the heteroatom is an aqueous solution or an organic solution with the mass percentage concentration of 15-25%.
4. The method for preparing a carbon aerogel supported cobalt monatomic catalyst for a metal-air battery according to claim 2, characterized in that: in the step (1), the cobalt precursor is one or more of cobalt-based ionic liquid, vitamin B12, cobalt porphyrin, cobalt phthalocyanine, a cobalt porphyrin-cobalt acetate complex, a cobalt-phenanthroline complex and sulfonated cobalt phthalocyanine; the cobalt precursor solution is an aqueous solution or an organic solution with the mass percentage concentration of 4-14%.
5. The method for preparing a carbon aerogel supported cobalt monatomic catalyst for a metal-air battery according to claim 2, characterized in that: in the step (1), the pore-forming agent is one or more of silicon dioxide, calcium carbonate, sodium carbonate, zinc chloride and sodium chloride; the mass fraction of the pore-forming agent is 1-5%.
6. The method for preparing a carbon aerogel supported cobalt monatomic catalyst for a metal-air battery according to claim 2, characterized in that: in the step (2), the chitosan hybrid aerogel consists of the following precursors in percentage by mass:
and (3) chitosan: 1 to 5 weight percent,
pore-forming agent: 1 to 5 weight percent,
heteroatom-containing precursors: 77 wt% -95 wt%,
cobalt precursor: 3 wt% -13 wt%.
7. The method for preparing a carbon aerogel supported cobalt monatomic catalyst for a metal-air battery according to claim 2, characterized in that: in the step (3), the inert atmosphere is high-purity nitrogen or high-purity argon; the high-temperature carbonization comprises the following steps: the first step is as follows: heating the mixture from room temperature to T, wherein T is 700-1000 ℃, the heating rate is 4-8 ℃/min, and the second step is as follows: keeping the temperature T constant for 1-3 h, and the third step: and cooling the temperature from T to room temperature at a cooling rate of 4-10 ℃/min.
8. The method for preparing a carbon aerogel supported cobalt monatomic catalyst for a metal-air battery according to claim 2, characterized in that: in the step (4), the acid solution is at least one of hydrofluoric acid aqueous solution, hydrochloric acid aqueous solution, nitric acid aqueous solution and sulfuric acid aqueous solution; the acid solution is 0.5-2 mol/L, the acid soaking time is 12-24 h, and the acid soaking temperature is 60-100 ℃.
9. The use of the carbon aerogel-supported cobalt monatomic catalyst for metal-air batteries according to claim 1, in electrocatalytic oxygen reduction.
10. A metal-air battery comprises an air anode, a diaphragm, electrolyte and a metal cathode, wherein the air anode comprises a gas diffusion layer, a current collector layer and a catalyst layer, and is characterized in that: the catalyst is the carbon aerogel supported cobalt monoatomic catalyst for metal-air batteries according to claim 1.
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| CN113584514A (en) * | 2021-08-27 | 2021-11-02 | 中国人民解放军国防科技大学 | Preparation method of monoatomic metal-nitrogen doped carbon aerogel electrocatalyst |
| CN113937307A (en) * | 2021-09-10 | 2022-01-14 | 华中科技大学 | Silicon-doped non-noble metal fuel cell cathode catalyst and preparation method thereof |
| CN114284512A (en) * | 2021-12-29 | 2022-04-05 | 吉林大学 | Preparation method of carbon molecular sieve-cobalt monoatomic catalyst for zinc-air battery |
| CN114887639A (en) * | 2022-04-19 | 2022-08-12 | 东莞理工学院 | Novel CO 2 Reduction catalyst, application and preparation method thereof |
| CN114990567A (en) * | 2022-05-13 | 2022-09-02 | 北京理工大学 | Preparation method and application of sulfur coordination cobalt monoatomic catalyst loaded on carbon-based carrier |
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| CN113584514B (en) * | 2021-08-27 | 2022-08-19 | 中国人民解放军国防科技大学 | Preparation method of monoatomic metal-nitrogen doped carbon aerogel electrocatalyst |
| CN113584514A (en) * | 2021-08-27 | 2021-11-02 | 中国人民解放军国防科技大学 | Preparation method of monoatomic metal-nitrogen doped carbon aerogel electrocatalyst |
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| CN113937307B (en) * | 2021-09-10 | 2023-03-14 | 华中科技大学 | Silicon-doped non-noble metal fuel cell cathode catalyst and preparation method thereof |
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| CN114990567A (en) * | 2022-05-13 | 2022-09-02 | 北京理工大学 | Preparation method and application of sulfur coordination cobalt monoatomic catalyst loaded on carbon-based carrier |
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